Production of tio2 pigments



Patented 5,1943:

' STATES PAr1:-: Nr or-ms rnonvc'llorf zfl zh PIGMENTS I John Lewis Keats, Wilmington, DeL',

E21. du Pont de-Nemours a Company, W

aselgnor to ton, Del., a corporation of Delaware 1 l lo-Drawing.

Application September 15, 1989, Serial No.'295,049

11 Claims. (Ci. za-zoz) This invention relates to the production of improved titanium oxide. pigments and more particularly to a novel method for improving the brightness and'other pigmentaryv qualities of such substances.

More specifically, the invention relates to the production oftitanium oxide pigments exhibiting improved brightness, color and tinting strength and possessing substantially the x-ray diffraction pattern of rutile.

0n hydrolysis, titanium a raw T: pigment product which'possesses the X-ray diffraction pattern of anatase. On calsulfate solutions yield cination, this raw pigment loses'its volatile'con tent (moisture and sulfuric acid and undergoes various changes, among others, growth of crystal size and change in particle size, Calcination is conducted under relatively controlled temperature conditions and in order to develop optimum pigment qualities, particularly tinting strength and color. It the temperature of calcination is suificiently high, the anatase crystals will be converted more or less to rutile, which has a refractive index higher than anatase. However, the temperature which is'required to effect such conversion is so high thata serious sacrifice occurs in ,pigment properties, particularly colorv and bright'nessp Also, an objectionable loss is had in tinting strength, due to excessive growth of par- -:-::;'Ihe addition oi certain treating agents, particularly the salts of sodium and potassium, to raw pigment anatase prior to calcinatlon to improve Eithe -quality of the final pigment, has already been suggested. However, potassium salts are relativeinhibitors'of rutile formation. For inture's of -the order of substantially 1000 C., the anatase crystal form is retained. Sodium salts also act as effectiveinhibiting agents against rutile formation, though to a somewhat lesser ex-. tent. Ineither event, however, should the calcination "temperature be increased to a point where rutile is formed (well above 1000 C.) the final pigment product will be found to be greyish minor quantities'thereof, an entirely different result is procured. I have found that lithium saltsnot only fail to inhibit rutile formation during calcination, but they usually actually catalyze the conversion from anatase. It ismy further I discovery that calcinaticns in the presence of lithium salts need only be conducted at relatively moderate temperatures to effect such conver- 'sion to rutile: and that thereby such conversion can be readily effected, in wholeor in part, without any objectionable sacrifice in the pigment properties of the final product, particularly alteration of particlesize and consequent reductionin tinting strength and hiding power, or sacrifice in color or brightness.

It is accordingly among the objects of this invention to provide a novel process for; the

preparation of titanium oxide pigments of s'u periorbrightness, color and high tinting strength.

A further object is the preparation of titanium f oxide pigments in the rutile crystalline form and through means of calcination at relatively moderate temperatures. A'still further object is the preparation of titanium oxide pigments in the rutile crystalline form, characterizedby high tinting strength and superior brightness and co or.

These and other objects are accomplished in this invention which comprises subjecting precipitated anatase titanium-oxide to calcination in the presence of a lithium salt as a rutile conversion accelerator.

In a more specific and preferred embodiment, the invention comprises subjecting precipitated raw anatase TiO2 from the hydrolysis of a titanium sulfate solution to calcination at a relatively moderate temperature in the presence of a relatively small amount of a lithium salt adapted to catalyze the conversion of said anatase to rutile during such calcination.

In one practical and preferred adaptation of the invention, the product obtained from the hydrolysis of a titanium sulfate solution (such as the type of product resulting from the hydrolysis procedures described in U. S. Reissue Patent 18,854), after being suitably washed to displace the mother liquor, is intimately mixed, in any desired manner, with a relatively smallj amount, say,'about 1%, calculated on thepig'ment basis, 01' a lithium compound, preferably an inorganic soluble salt, such as lithium sulfate; Admixture of the precipitate and salt can be conveniently jected to drying'and calcination,'said calcination being effected at temperatures in excess'of substantially 800 (2., and preferably within the range of from about 900 to 950 C., to develop optimum pigment qualities in the final product. The calciner discharge may be suitably treated, e. g.. by washing to remove soluble salts, in accordance with conventional pigment processing methods. The final product comprises a, high-quality pigment substanc which, when tested in accordance with well-known X-ray methods, will be found to comprise titanium oxide in substantially the crystalline structure of rutile.

In order that the invention may be more clearly understood, the following specific examples are given, each being merely in illustration and in limitation of the invention:

EXAMPLE I Titanium sulfate solution prepared by attacking ilmenite'with H2804 was hydrolyzed as follows: 3030 cc. of a solution containing 297 g. TlOz, 42.0 g. Fe and 710 g. H2804 per liter was heated to 97 C., and was then run at a uniform rate during aperiod of minutes into a vessel connot I taining 1000 cc. of waterheld at 92 C. A turbidity appeared during the first few seconds of the mixing which later disappeared. After the addition of the titanium sulfate solution to the diluent was complete the diluted solution was raised to the boiling point of the solution (109 C.) and boiled for a period of 3 hours. The raw pigment precipitate was washed in the usual manner to remove iron and other impurities. The wet filter cake was divided into two parts, to one of which was added an amount of lithium sulfate, Li2SO4.H2O, equivalent to 1% on the TiO2 basis. The two portions were dried separately and caloined at temperatures of 950 and 1000 C. The

samples which were calcined at 950 C. were of the anatase crystal form. The one which was treated with lithium sulfate was distinctly superior to the untreated product as regards both tinting strength and color. Of the products calcined at 1000 C. the one which was treated with lithium sulfate contained 75% rutile while the one not salttreated contained only 50% rutile.

The lithium salt-treated product was graded 6 i in color compared with for the untreated product. The foregoing facts are summarized in.

the following table:

950 C. calcination 1000 C. calcination 535 2 strength Color gi Color N on exit treat- Anatase..- 380 6 50% rutile.-- 6 1% Li:SO|.HgO d0 530 11 75% rutile.-- ll EXAMPLE II Titanium oxide raw pigment was prepared by hydrolysis of titanium sulfate solution as follows: 2030 cc. of a solution of titanium sulfate containing 294 grams TiOz and 71 grams Fe per liter was run into 200 cc. of water heated to 92 C. in a period of 14 minutes. The resulting solution was heated to boiling and boiled for a period of 3 hours at a concentration of 225 grams T10: per liter. The precipitate from the hydrolysis was washed in the usual manner to remove iron and other impurities. The washed raw pigment was divided into two equal parts into one or which was incorporated lithium sulfate equivalent to 1% Li2SO4.H2O on the "T10: basis. The products were dried at a temperature of 100 C. and the dried products calcined for a periof of minutes at a temperature of 950 C. The product containing lithium sulfate was all rutile after calcination and was characterized by a color of 13+ while the product not containing lithium sulfate was rutile after calcination and was given a color grading of 4.

The color and brightness determinations herein referred to were obtained in accordance with the methods described by J. E. Booge and H. E. Eastlack in the Paint, Oil and Chemical Review. April 9, 1924.

To demonstrate more particularly the benefits which are derivable in the invention, especially as regards increase in rutile conversion and impartation of improved color and-brightness to the final pigment product, the following table is given, showing the results of calcination of different raw pigments prepared under different hydrolysis conditions. Results are shown for each pigment, both with and without lithium salt treatment:

Table I Pig- Crystal ment Salt treatment form As will be evident, in each instance the lithium salt-treated TiOz showed a decided improvement in brightness and increase in rutile content over the untreated control sample.

By employing larger quantities of lithium salts during the calcination treatment, it will be found that rutile formation becomes desirably increased, as is evident from the data in the ensuing table, also based on the treatment of an anatase precipitate from a titanium sulfate hydrolysis:

Table II Pi Calcina C I tion rysta ment Salt treatment temper form ature 1.. 10% LlzCOs.

As will be apparent from the data given above,

. alkalimetais such as,

. 2,807,048 diflerent salts of lithium areeiicetive inlowering templating the use only of such alkali salts as thoconversiontemperatureoitheanataseto thoseofsodiumand unallotonly'arc rutile and for imparting the desired requisite brightness and color characteristics to thevwfinal product.- Although mentioned salts comprise those preferred for use, all type oi. lithium compounds may be used herein, particularly the inorganic soluble salts. especially the sulfate, halide, chlorate, carbonate, nitrate, etc" alone or in admixture with other lithium salts or with other for instance, in the commonly occurring minerals which contain lithium. While the soluble lithium salts are especially preferred. those which are relatively insoluble in character may also be employed. a

Again, while reference has been made and use had of specific amounts oi treating agents, the invention is not limited to such amounts. In general. use is contemplated compounds rangin from substantially 0.2% to 1096 or higher. In most instances the addition oi about 1.0% oi. lithium salt calculated on the pigment basis, will be found suiiicient to cause an appreciable lowering oi the temperature oi. conversion and as an eifective quantity for improving the tinting strength and brightness even at calcination for effecting such conversion. Also, though calcination temperatures in excess of 800' 0., and specifically of the order of 850' to 1000' 0., have been shown to be utilizable', even higher temperatures may be employed, and always with improved quality of product over that obtained by calcination at the same temperature of a pigment which is the same except that no lithium saltispresent.

As has been indicated, salts in accordance with found that they not only assist in effecting formation of rutile, but actually catalyze the conversion. Furthermore, tures greatly in excess of 1000' C. have been required to effect such conversion, in the instant invention the calcination temperature required to develop optimum pigment properties is considerably reduced. An important factor in the invention resides in the discovery that at these relatively moderate (QM-1000 C.) calcination temperatures the lithium-treated product becomes converted wholly or in major amount to rutile and without objectionable alteration of particle size or appreciable sacrifice in color. As a result. a rutile type titanium oxide pigment is produced which exhibits much higher tinting strength and hiding power than those of the anatase type, and

by the use of lithium temperatures well below those ordinarily the invention it will be".

due to the direct relationship between these pigment properties and refractive index.

The invention embodies the discovery therefore that lithium salt treatment of titanium oxide pigment filter cake is specific in permitting calcinations at a, temperature high enough to obtain conversion from anatase torutile without at the same time encountering (1) objectionable sintering with its detrimental effect on particle size. and (2) serious loss of color. It also embodies the discovery that lithium salt treatment of titanium oxide raw pigment, followed by calcinatlon at temperatures lower than are required for conversion from anatase to rutile, yields rutile products of improved strength and color. Thus, the treatment of the raw pigment from a sulfate hydrolysis with lithium salts to increase the rutile content and improve the brightness of the calcined products is distinctly an improvement over prior procedures, and especially those conlithium salts effective in promoting rutile iormaw tion, but at the same time they improve the brightness and color 0! the final product.

I claim as my invention:

l. A process for producing pigment exhibiting substantially fraction patternpf rutile,.comprising-subiecting a of amounts of lithium I pigment comprising calcining 40 while heretofore temperacalcination an added washed TiOa hydrolysis precipitateto in the presence of a small amount of lithium salt.

2. A process ior producing a titanium oxide pigment exhibiting substantially the x-ray diffraction pattern of rutile. comprising subjectin v the washed precipitate obtained from the hydrolysis of a titanium sulfate solution to calcinetion in the presence of a small amount of a lithi-' um salt added to said precipitate.

3. A process for producing atitanium oxide pigment exhibiting substantially the X-ray diffraction pattern-of rutile, comprising subjecting washed precipitated anatase titanium oxide to calcination in the presence 01 from about 0.2% to about 10%, on the pigment basis, of a lithium salt added to said precipitate.

.A. -A process for producing a. titanium oxide pigment exhibiting subst'antiailythe x-ray dilfraction pattern of rutile, comprising subjecting washed precipitated anatase titanium oxide to calcination in the presence of from 1% to 10%, on the pigment basis, of a lithium salt added to said precipitate.

cipitated anatase titanium oxide in the presence of added lithium sulfate.

6.- A process for producing rutiletitanium oxide washed precipitated anatase titanium-oxide in the presence of from about 1 to 10% of added lithium sulfate.

7. A process for producing rutile titanium oxide pigment comprising calcining washed precipitated anatase titanium oxide in the presence of about 1% of added LiiSQimO.

8. A process for producing rutile titanium oxide pigment comprising calcining washed precipitated anatase titanium oxide in the presence of added lithium chloride.

9. A process for producing rutile titanium oxide pigment of improved brightness and color and through conversion of precipitated washed anatase titanium oxide, comprising subjecting said anatase modification to calcination at temperatures ranging from'substantially 800 to 1000 0., in the presence of a small amount of a soluble salt of lithium added to said anatase titanium oxide.

10. A process for producing rutile titanium oxide pigment of improved brightness and color and through conversion of anatase titanium oxide, comprising subjecting said anatase modification to calcination at temperatures ranging'from substantially 800 to 1000 C.. in the presence of from .02 to 10% of added lithium sulfate.

ii. A process for producing rutile titanium oxide pigment of improved brightness and color and through conversion of precipitated, washed anatase titanium oxide, comprising subjecting said anatase modification to calcination at temperatures ranging from substantially 850 to 1000 C., in the presence of from about 1 to 10% of an added inorganic soluble salt of lithium.

JOHN LEWIS KEATS.

k CERTIFICATE OF CORRECTION.

; Jonnmwxs mus.

signed end 'se aled thig 2nd. day 0: March, 1),; 4;

. I Henry Van trs dt lle )w (Seal) I hqtmg comnissioherpf Patents. 

